This invention relates to mixtures of disperse dyes, compositions comprising dispersions of such mixtures and processes for the colouration of synthetic materials with such mixtures. More particularly, the invention relates to mixtures of reddish blue monoazo dyes with those of the so called pyrroline type, which tend to be greenish blue.
Monoazo dyes of the above type are disclosed in EP-A-0300626 and EP-A-0347685.
As a component of a mixture of dyes, EP-A-0300626 discloses a dye of the formula 
where X is Br, Cl or I; Q is C1-4alkyl; and each of R1 and R2 independently is C1-4alkyl or C2-4alkenyl.
Similarly, as a component of a mixture of dyes, EP-A-0347685 discloses a dye of the formula 
wherein Y is NO3 or CN, R1 is alkyl aralkyl alkoxyalkyl or alkenyl and R2 is alkyl, aralkyl, alkoxyalkyl, alkenyl, chloroalkyl, aryloxyalkyl or alkoxycarbonyalkyl. Such dyes are in admixture with, for example, monoazo-dyes containing a thiophene nucleus.
WO-A-97004030 discloses mixtures of the following dye with a thiophene dye in various proportions. 
Dyes of the abovementioned pyrroline type are disclosed, for example, in U.S. Pat. No. 3,013,013, U.S. Pat. No. 3,013,018, GB-A-2191498, EP-A-0327077, EP-A-0511625 and WO-A-94010248.
In particular, WO-A-94010248 discloses dyes of the pyrroline type having the formula (1). 
wherein:
D is a group of the Formula (2) 
xe2x80x83or a group of Formula (3): 
xe2x80x83or a group of the Formula (4) 
R1 is alkyl, cycloalkyl, aryl, a kenyl or aralkyl each of which may be optionally substituted;
R2 is optionally substituted C7-20-alkyl; or
R1 and R2 together with the nitrogen atom to which they are attached form a pyrrolidino or piperidino ring;
R3 is alkyl, alkenyl or aralkyl each of which may be optionally substituted, xe2x80x94SO2alkyl, xe2x80x94SO2aryl, or xe2x80x94COR in which R is xe2x80x94H or alkyl, phenyl, cycloalkyl or aralkyl each of which may be optionally substituted or xe2x80x94H; and
R4 is an electron withdrawing group;
R6 is optionally substituted C1-14-alkyl; or
R1 and R6 together with the nitrogen atom to which they are attached form a pyrrolidino or piperidino ring;
R7, R8, R9 and R11 each independently is alkyl, cycloaklyl, aryl, alkenyl or aralkyl, each of which may be optionally substituted, or xe2x80x94H;
W is oxygen or sulphur;
Z is a direct link or Nxe2x80x94R11 in which R11 is xe2x80x94H or optionally substituted alkyl or aryl;
Ring A is unsubstituted apart from the xe2x80x94NR1R2 group or is substituted by from 1 to 4 further groups; and
Ring B is unsubstituted or substituted by from 1 to 3 groups; except for 3-(4-(N,N-di-n-octylamino)phenyl)-4-cyano-5-dicyano methylidene-2-oxo-2,5-dihydropyrrole
provided that:
(a) when D is a group of Formula (3), R1 and R6 are different and R1 is not xe2x80x94C2H5, xe2x80x94C3H7 or xe2x80x94C1H9 when R6 is xe2x80x94C2H4phenyl, xe2x80x94C3H6phenyl and ethyl substituted by xe2x80x94OH, xe2x80x94CN, xe2x80x94OCH3, xe2x80x94OC2H4OC2H5, xe2x80x94NHCOCH2 xe2x80x94Ophenyl and xe2x80x94NHSO2CH3; or
(b) at least one of R1 and R6 is branched chain alkyl. Commercially available dyes of the pyrroline type are, for example, dyes of the formula: 
xe2x80x83where RA is H (Kayalon Polyester Brilliant Blue F2B-S); or CH2CHxe2x95x90CH2 (Kayalon Polyester Blue-Green FG-S); and dyes of the formula 
xe2x80x83where XA is C4H9 and YA is CH(CH3)C5H11.
It is found that certain mixtures, although giving bright shades on polyester when viewed in normal daylight, tend to exhibit a xe2x80x9credxe2x80x9d flare in tungsten light which is a serious commercial disadvantage.
Although the problem of xe2x80x9cflarexe2x80x9d may be solved by at least one of the mixtures disclosed in EP-A-0347685, such a mixture is especially sensitive to reduction and has a relatively low heat fastness. Likewise flare can be avoided by using a dye mixture in which the nitrothiophene carries an acetyl group. However, such dyes tend to be expensive.
We have found surprisingly that a mixture of dyes, as defined below, surprisingly not only allows reduction or even elimination of the xe2x80x9credxe2x80x9d flare, but provides a much brighter shade and is less sensitive to reduction with consequent loss of shade.
Thus, the invention provides a mixture of dyestuffs containing at least
(A) at least one monoazo dye of the formula (I) 
xe2x80x83wherein XA is Cl, Br, I, CN or NO2;
RA is C1-4alkyl (or NHCOQ, where Q is C1-4alkyl); and
each of RA1 and RA2 independently is C1-4alkyl, C2-4alkenyl, C1-4-alkoxy C1-4alkyl, aryl-C1-4alkyl or aryloxy-C1-4alkyl; and
(B) at least one dye of the formula (II) 
xe2x80x83wherein RB1 is H, C1-20alkyl or C2-20alkenyl; and
D is aryl.
In a preferred dye mixture, in a dye of the formula (I) of the mixture, an especially preferred value of XA is Br or CN, especially preferred values of RA are NHCOCH3, NHCOC2H5, CH3 and C2H5 and especially preferred values RA1 and RA2 are methyl, ethyl and allyl.
Typical especially preferred components (A) in mixtures embodying the invention are selected from
(A1)a monoazo dye of the formula (I), wherein XA is Br, RA is NHCORX where RX is methyl or ethyl and each of RA1 and RA2 is ethyl;
(A2)a monoazo dye of the formula (I wherein XA is CN, RA is CH2 and each of RA1 and RA2 is ethyl; and
(A3) a monoazo dye of the formula (I), wherein XA is CN, RA is CH2, RA1 is methyl and RA2 is 3-phenylpropyl.
The dyes of the formula (I) may be Prepared in a conventional manner by diazotisation and coupling.
More particularly, for dyes wherein, in formula (I), XA is Cl, Br or I, an amine of formula (III) 
xe2x80x83wherein X is
Cl, Br, or I, is dlazotised and coupled with a coupling component of the formula (V) 
xe2x80x83wherein RA, RA1 and RA2 are as defined above
Dyes of the formula (I), wherein XA is CN may be prepared by diazotizing 2,6-dibromo-4-nitroaniline and coupling to a coupling component of the formula (V) to form a precursor dye and thereafter subjecting the precursor dye to a copper catalysed cyano exchange reaction using, for example, copper cyanide or a mixture of copper and sodium cyanides, optionally in a solvent such as dimethyl formamide.
Similarly, dyes of the formula (I), whereon XA is NO2 may be prepared by diazotizing 2-dibromo-4,6-dinitroaniline, coupling to a coupling component of the formula (V) and then subjecting the resulting precursor dye to the above copper catalysed cyano exchange reaction.
In the above diazotisation and coupling reactions, the diazotization is carried out using a diazotising agent, which is preferably nitrosyl sulphuric acid, optionally diluted with glacial acetic acid or a phosphoric/acetic acid mixture and preferably at a temperature of 0-10xc2x0 C., more preferably 0-5xc2x0 C. and preferably at a pH less than 1 (say 0.5) up to 7, more preferably 0.5-1, followed by a subsequent increase in pH to 3-4 to isolate the dye.
Reference is now made to component (B), which comprises a pyrroline type dye of the formula (II).
In the compound of the formula (II), D is preferably a group of the formula (a). 
wherein each of RB2 and RB3 independently is alkyl, cycloalkyl, aryl, alkenyl or aralkyl.
In the above formula (II), the alkyl group represented by any of RB1-RB3 is preferably a C1-20-alkyl, more preferably a C1-12-alkyl and especially a C1-8-alkyl, group. The cycloalkyl group represented by RB2 or RB3 is preferably a C4-8-cycloalkyl and more preferably a cyclohexyl group. The aryl group represented by RB2 or RB3 is preferably phenyl. The alkenyl group represented by any of RB1-RB3 is preferably a C2-10-alkenyl, more preferably C2-6-alkenyl and especially a C2-3-alkenyl group, such as allyl. The aralkyl group represented by any one of RB1-RB3 is preferably a phenyl-C1-6-alkyl, more preferably a phenyl-C1-3-alkyl, especially phenylethyl or 3-phenylpropyl.
The alkyl group represented by RB3 is more preferably a C7-15-alkyl, still more preferably a C7-12-alkyl and especially a C7-9-alkyl group.
The alkyl group represented by RB1 is more preferably a C1-6-alkyl and still more preferably C1-4-alkyl group.
RB1 is especially preferably xe2x80x94H, C1-4-alkyl or C2-3alkenyl, more preferably xe2x80x94H or C1-4-alkyl and especially xe2x80x94H.
D is preferably a group of Formula (a).
The alkyl groups represented by any of RB1-RB3 may be straight or branched chain alkyl groups. RB2 is preferably C1-12-alkyl more preferably C1-8-alkyl especially unsubstituted C1-8alkyl. RB3 may be C7-12-alkyl and preferably C7-9-alkyl, especially unsubstituted C7-9-alkyl or may be unsubstituted C1-6-alkyl. Where D is a group of Formula (a) it is preferred that one or both of RB2 and RB3 is branched, more preferably branched at an xcex1- or xcex2-, i.e., 1- or 2-, position. It is preferred that RB2 and RB3 are different. It is also preferred that ring A is unsubstituted apart from the NRB2RB3 group.
A preferred sub-group of dyes of Formula (I) is that in which D is a group of Formula (a):
RB1 is alkyl or xe2x80x94H;
RB2 is alkyl;
RB3 C7-20-alkyl; and
Ring A is unsubstituted apart from the NRB2RB3 group.
Another preferred sub-group of dyes of Formula (II) is that in which D is a group of the Formula (a);
RB1 is xe2x80x94H or alkyl;
RB2 is unsubstituted C1-8-alkyl;
RB3 is unsubstituted C1-6-alkyl;
Ring A is unsubstituted apart from the xe2x80x94NRB2RB3 group; and RB2 and RB3 are different or at least one of RB2 and RB3 is a branched chain alkyl.
An especially preferred sub-group of dyes of Formula (II) is that in which D is a group of Formula (a):
RB1 is xe2x80x94H;
RB2 is unsubstituted C1-8alkyl;
RB3 is unsubstituted C7-9alkyl; and
Ring A is unsubstituted apart from the NRB2RB3 group.
A further especially preferred sub-group of dyes of Formula (II) is that in which D is a group of Formula (a);
RB1 is xe2x80x94H;
RB2 is n-propyl or n-butyl;
RB3 is 1-methylhexyl or 2-ethylhexyl; and
Ring A is unsubstituted apart from the xe2x80x94NRB2RB3 group;
Typical especially preferred mixtures of components (B) in mixtures embodying the invention are selected from
(B1) a pyrroline type dye of the formula (II), wherein RB1 is H, RB2 is C4H9 and RB3 is 1-methyl-n-hexyl (B1) or a mixture thereof with up to 10%, by weight of component (B1), of a pyrroline type dye B2) of the formula (II), wherein RB1 is H and each of RB2 and RB2 is C4H9;
(B2) a pyrroline type dye of the formula (II), wherein RB1 is H, RB2 is ethyl and RB3 is n-octyl (B3), or 2-ethyl-n-hexyl (B4) or a mixture of dyes (B3) and (B4); and
(B3) a pyrroline type dye of the formula (II), wherein RB2 is C4H9, RB3 is phenylpropyl and RB1 is H (B5) or allyl (B6) or a mixture of dyes (B5) and (B6).
When RB1 is H, dyes of Formula (II) may exist in a tautomeric form represented by Formula (IIA): 
wherein D is as hereinbefore defined.
The dyes of Formula (II) where D is a group of Formula (a) may be prepared by reaction of an aniline of Formula (III): 
in which Ring A is as hereinbefore defined, firstly with a compound of Formula RB2XB in which RB2 is as hereinbefore defined and XB is a halogen such as xe2x80x94Cl, xe2x80x94Br or xe2x80x94I or other leaving group, such as a tosylate, mesylate or alkylsulphonate, in the presence of a base such as an alkali metal carbonate or alkaline earth metal carbonate such as K2CO3 or CaCO3 and secondly with a compound of formula, RB3X in which RB3 and X are as hereinbefore defined in the presence of a base as above to form an aromatic amine of Formula (IV); 
Alternatively the aromatic amine of the Formula (IV) may be prepared by reductive alkylation of the aniline of Formula (III) with an appropriate ketone or aldehyde. The reductive alkylation may be performed in an inert liquid medium such as an alcohol or ester optionally in the presence of an acid such as an aliphatic carboxylic acid, for example, acetic and propionic acids and aromatic sulphonic acid e.g. 4-toluenesulphonic acid using a metal or supported metal catalyst such as palladium or platinum on carbon and hydrogen, optionally at elevated temperature and pressure. Alternatively, reducing agents such as sodium borohydride may be used. After the reductive alkylation a second alkyl group may be introduced as described above.
The aromatic amine of Formula (IV) is then reacted with a 3-halopyrrole of Formula (V): 
in which RB1 is as hereinbefore defined and XB is preferably a halogen such as xe2x80x94Cl or Br to form a compound of Formula (II). The reaction may be performed in a liquid medium such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulphoxide, suldholane, N-methylpyrrolidone, acetonitrile, toluene or tetrahydrofuran or any mixture thereof and at a temperature from xe2x88x9220xc2x0 C. to 50xc2x0 C. The product may be isolated by any convenient means such as pouring the reaction mixture into a mixture of ice and water and recovering the precipitated product by filtration. The product may be purified by any convenient means such as trituration or recrystallisation from organic liquids particularly alkanols such as methanol, ethanol and esters such as ethylacetate or mixtures thereof.
The 3-halo-2-oxopyrrole of Formula (V) may be prepared by halogenation of a compound which may be represented by Formulae (VI), (VI1) and (VI2) 
with a halogenating agent such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride or phosgene at a temperature of from xe2x88x9220xc2x0 C. to 50xc2x0 C. in a liquid medium such as N,N-dimethylformamide, N,N-diethylacetamide, dimethylsulphoxide, sulpholane, N-methylpyrrolidone, acetonitrile or tetrahydrofuran. The product may be used without isolation with improvement in yield in the preparation of compounds so Formula (II) described above or may be isolated by evaporating the liquid medium.
Alternatively a compound of Formula (IV) may be reacted directly with the compound represented by Formulae (VI), (VI1) or (VI2) in a liquid medium such as toluene in the presence of a halogenating agent such as phosphorus oxychloride.
The compounds represented by Formulae (VI) or (VI1) may be prepared by reaction of diethyloxalate with a compound for Formula (VII); 
in the presence of a base such as an alkali metal alkoxide preferably a sodium or potassium C1-6-alkoxide and especially sodium or potassium methoxide, ethoxide, n- or iso-propoxide, n-, iso- or, tertiary-butoxide in a liquid medium, preferably an alkanol such as methanol, ethanol, n- or iso-propanol or n-, iso- or tertiary-butanol, at a temperature of from 10xc2x0 C. to 60xc2x0 C. The product may be isolated by cooling the reaction mixture and collection by filtration.
The compound of Formula (VII) may be prepared by dimerization of malononitrile of Formula (VIII):
NCCH2CNxe2x80x83xe2x80x83Formula (VIII)
by reaction with a base such as sodium methoxide in a liquid medium such as methanol at a temperature of from xe2x88x9220xc2x0 C. to 60xc2x0 C. The product may be isolated by filtration.
A dye of Formula (II) in which RB1 is other than xe2x80x94H may be prepared by reaction of the corresponding dye of Formula (II) in which RB1 is xe2x80x94H in a liquid medium, preferably an amide such as dimethylformamide or an ether such as tetrahydrofuran or diethylether in the presence of a base, preferably an alkali metal carbonate such as potassium carbonate or an alkali metal hydride such as sodium hydride at a temperature of 0xc2x0 C. to 120xc2x0 C. with an appropriate alkylating or acylating agent. Where RB1 is alkyl an appropriate alkylating agent is an alkyl halide, preferably an alkyl iodide, bromide or chloride. Where RB1 is alkenyl an appropriate alkylating agent is an alkenyl halide, preferably an alkenyl bromide. These dyes may be isolated by evaporating the liquid medium or by filtration from the reaction mixture.
As previously mentioned, component (B) may be a mixture of two or more dyes of Formula (II) wherein RB1 to RB3 inclusive, D and Ring A are as hereinbefore defined.
In general, in a preferred mixture of components (A) and (B), the ratio, by weight, of component (A): component (B) may be from 95:5 to 80:20 inclusive, for example from 85:15 to 35:65 inclusive, or from 70:30 to 40:60, depending upon the choice of dyestuff.
In especially preferred mixtures of components (A) and (B), component (A) is selected from,
(A1) a monoazo dye of the formula (I), wherein XA is Br, RA is NHCORX where RX methyl or ethyl and each of RA1 and RA2 is ethyl;
(A2) a monoazo dye of the formula (I), wherein XA is CN, RA is CH3 and each of RA1 and RA2 is ethyl; and
(A3) a monoazo dye of the formula (I), wherein XA is CN, RA is CH3, RA1 is methyl and RA2 is 3-phenylpropyl; and component (B) is selected from
(B1) a pyrroline type dye of the formula (II), wherein RB1 is H, RB2 is C4H9 and RB3 is 1-methyl-n-hexyl (B1) or a mixture thereof with up to 10%, by weight of component (B1), of a pyrroline type dye (B2), of formula (II), wherein, RB1 is H, and each of RB2 and RB3 is C4H9; or
(B2) a pyrroline type dye of the formula (II), wherein RB1 is H, RB2 is ethyl and RB3 is n-octyl (B3), or 2-ethyl-n-hexyl (B4) or a mixture of dyes (B3) and (B4); or
(B3) a pyrroline type dye of the formula (II), wherein RB2 is C4H9, RB3 is 3-phenylpropyl and RB1 is H (B5) or allyl (B6) or a mixture of dyes (B5) and (B6).
Especially preferred compositions are the following two component mixtures:
(1) Component (A1) 
xe2x80x83where R is CH3 and/or C2H5.
[the dye wherein R is ethyl is commercially available as C.I. Disperse Blue 183]; and
Component (B1) 
xe2x80x83[which dye may contain up to 10% by weight of the corresponding N,N-dibutyl compound];
(2) Component (A2) 
xe2x80x83[available commercially as C.I. Disperse Blue 366] and Component (B1) 
xe2x80x83[as in the above mixture]; and
(3) Component (A3) 
xe2x80x83[commercially available as C.I. Disperse Blue 368] and
Component (B1) 
xe2x80x83[as in each of the above mixtures].
More especially preferred are mixture (1) of components (A1) and (B1) in the ratio of 30:10 to 60:40 by weight, mixture (2) of components (A2) and (B1) in the ratio of 70:30 to 40:60 by weight and mixture (3) of components (A3) and (B1) in the ratio of 70:30 to 40:60 by weight.
A mixture embodying the invention of at least one dye of formula (I) (Component A) and at least one dye of the formula (II) (Component B) may additionally comprise at least one other dye (Component C), especially a yellow, orange, red or brown dye capable of producing a navy or black shade.
Mixtures embodying the invention can be prepared by a number of methods including
(1) Co-crystallisation
Typically, the dyes are dissolved in a hot solvent, for example, by placing the dyes in a suitable solvent and heating up to the reflux temperature of the solvent until the dyes are dissolved, thereafter filtering to provide a solution, and then allowing the solution to cool and crystals to form. The resultant mixture may then undergo further processing, such as milling and spray drying. Examples of suitable solvents for this process are organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulphoxides, esters, ketones and ethers. Specific examples of organic solvents are toluene, ethyl cellosolve, acetone, chlorobenzene, pyridine, dimethyl formamide, dimethylsulphoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexane.
(2) Co-milling
(a) The dyes are mixed and then milled together to give an intimate blend which is then spray dried to give a solid mixture; or
(b) each dye is milled separately and then mixed in the required ratio before spray drying.
(3) Dry Blending
Each dye is spray dried separately and then mixed in the required ratio by a dry blending process.
The mixtures give an especially bright shade without exhibiting a red flare in tungsten light. The mixtures have high colour strength and can be readily and cost-effectively formulated.
Mixtures embodying the invention provide especially useful disperse dyes valuable for colouring synthetic textile materials and fiber blends thereof by exhaust dyeing, padding or printing, and may be formed into dispersions for this purpose. They may also be used in, for example, ink jet printing of textiles and non-textiles, dye diffusion, thermal transfer printing and in the colouration of plastics.
According to other aspects, the invention provides a composition comprising at least the dye mixture and a dispersing agent, surfactant or wetting agent, suitable for providing such a dispersion and also a process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material or fibre blend a mixture comprising at least one dye of the formula (I) and at least one dye of the formula (II).
The synthetic textile material may be selected from aromatic polyester, especially polyethylene terephthalate, polyamide, especially polyhexamethylene adipamide, secondary cellulose acetate, cellulose triacetate, and natural textile materials, especially cellulosic materials and wool. An especially preferred textile material is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned textile materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn or woven or knitted fabrics.
The mixtures of dyes of formulae (I) and (II) optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends by processes which are conventionally employed in applying disperse dyes to such materials and fibre blends.
Suitable process conditions may be selected from the following
(I) exhaust dyeing at a pH of from 4 to 6.5, at a temperature of from 125xc2x0 C. to 140xc2x0 C. for from 10 to 120 minutes and under a pressure of from 1 to 2 bar, a sequestrant optionally being added;
(ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 190xc2x0 C. to 225xc2x0 C. for from 15 seconds to 5 minutes, a migration inhibitor optionally being added;
(iii) direct printing at a pH of from 4 to 6.5, at a temperature of from 160xc2x0 C. to 185xc2x0 C. for from 4 to 15 minutes for high temperature steaming, or at a temperature of from 190xc2x0 C. to 225xc2x0 C. for from 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120xc2x0 C. to 140xc2x0 C. and 1 to 2 bar for from 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye optionally being added;
(iv) discharge printing (by padding the dye on to the textile material, drying and overprinting) at a pH of from 4 to 6.5, migration inhibitors and thickeners optionally being added;
(v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 95xc2x0 C. to 100xc2x0 C. using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, sequestrants optionally being added; and
(vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 85xc2x0 C. for acetate or at a temperature of 90xc2x0 C. for triacetate and nylon for from 15 to 90 minutes, secuestrants optionally being added.
In all the above processes, the dye mixture may be applied as a dispersion comprising from 0.001% to 6, preferably from 0.005 to 4%, of the dye mixture in an aqueous medium.
A particular aspect of the invention provides a composition comprising a mixture of dyes (I) and (II), optionally at least one other disperse dye and, additionally, optionally at least one further ingredient conventionally used in colouring applications such as a dispersing agent, surfactant or wetting agent. The composition topically comprises from 1% to 65%, preferably 10 to 60%, more preferably 20 to 55%, of the total dye mixture in a liquid, preferably an aqueous, or solid medium. Liquid compositions are preferably adjusted to pH 2 to 7, more preferably pH 4 to 6.
Typical examples of dispersing agent are lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates, typical examples of wetting agent are alkyl aryl ethoxylates which may be sulphonated or phosphated and typical examples of other ingredients which may be present are inorganic salts, de-foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the dye mixtures. Netting agents may be used at from 0% to 20% on the weight of the dye mixtures.
The compositions may be prepared by bead milling the dye mixture with glass beads or sand in an aqueous medium. The compositions may have further additions of dispersing agents, fillers and other surfactants and may be dried, by a technique such as spray drying, to give a solid composition comprising from 5% to 65% of dyestuff.
In addition to the above-mentioned application processes, the dye mixtures may be applied to synthetic textile materials and fibre blends by ink-jet printing, the substrates optionally having been pre-treated to aid printing. For ink-jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of 1:99 to 99:1, more preferably 1:95 to 50:50 and especially in the range 10:90 to 40:60. The water-soluble organic solvent preferably comprises a C1-C4-alkanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, butane-2,3-diol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyl)sulphone or mixtures thereof.
The dye mixtures may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted.